Chlorophyll dentifrice compositions



United States Patent 3,137,632 CHLOROPHYLL DENTERICE COMPGSITIONS Robert Joseph Schiraldi, New York, N.Y., assignor to Colgate-Palmolive Company, Jersey City, N.J., a corporation of Delaware No Drawing. Filed Feb. 19, 1952, Ser. No. 272,525 7 Claims. (Ell. 167-93) The present invention relates to dentifrice compositions and has particular reference to dentifrice compositions containing water soluble alkali metal salts of chlorophyll.

Chlorophyll, the green coloring material found in plants, is a water insoluble phytyl methyl ester of a porphyrin derivative. The water insoluble material may be converted to a water soluble material by saponification, for example, with a water soluble alkali metal base. The product thus obtained is a water soluble alkali metal salt, i.e., a water soluble chlorophyll compound.

The ability of water soluble chlorophyll compounds to heal wounds has been recognized for some years. Recent published articles describing clinical work on persons suffering from gum diseases, i.e., peridontal disorders like gingivitis, pyorrhea, and trench mouth, have reported that these compounds are eminently successful in not only treating but in effecting cures of these diseases in many cases. The water soluble chlorophyll compounds appear to stimulate the normal formation of healthy granulation tissue and thereby accelerate the healing of cuts and abrasions in the gums and other tissues of the mouth.

More recent investigations demonstrate that the compounds are useful also in eliminating or at least in substantially reducing undesirable breath odors.

The Water soluble chlorophyll compounds may be introduced into the mouth advantageously by brushing the teeth with the aid of a dentrifrice composition containing the said compounds. Experimental determinations indicate, however, that Water soluble chlorophyll compounds are not released in water solutions from dentrifrice compositions which contain such chlorophyll compounds and polishing agents such as Water insoluble calcium compounds. Furthermore, these determinations indicate that the chlorophyll compounds are not released in the aqueous media of the human mouth when such dentifrice compositions are used for brushing the teeth.

The present invention is based upon the surprising discovery that dentifrice compositions containing water soluble chlorophyll compounds and water insoluble calcium compounds as polishing agents can be prepared from which the chlorophyll compounds are released when the compositions are employed in the aqueous media of the human mouth.

Broadly, the novel dentifrice compositions of the present invention comprise at least one water insoluble calcium compound, a water soluble chlorophyll compound, and a watersoluble material selected from the group consisting of alkali metal salts of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, citric acid, silicic acid, gluconic acid, and ethylene diamine tetraacetic acid. The pH of the compositions should be within the range of about to 11 based upon a 20% water slurry of the composition.

Representative examples of suitable water soluble -alkali metal salt materials which may be employed in the dentifrice compositions of this invention include mono--, di-, and tri-sodium phosphate, disodium pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, mono-, di-, and tri-potassium phosphate, dipotassium pyrophosphate, tetrapotassiurn pyrophosphate, potassium tripolyphosphate, sodium citrate, sodium gluconate, sodium silicate, potassium citrate, potassium gluconate, potassium silicate, etc. The alkali metal salts may be emfee.

ployed in amounts up to about 10%, preferably in amounts up to about 5% of the finished compositions by weight. The sodium salts are preferably used because of their relatively low cost.

The water insoluble calcium compounds used as polishing agents in the dentifrice compositions of this invention may be selected from a relatively large number of materials. Representative materials include, for example, calcium carbonate, calcium sulfate, anhydrous dicalcium phosphate, dicalcium phosphate dihydrate, commercial tricalcium phosphate, etc. If desired, these materials may be replaced in minor amounts by other Water insoluble materials, e.g., aluminum hydroxide, magnesium carbonate, etc. The water insoluble polishing agent should be incorporated in the compositions in an appreciable amount and preferably should constitute the major proportion of the compositions, amounting to about 20% to by Weight of the finished dentifrice by weight.

The Water soluble chlorophyll compounds used in the dentifrice compositions herein described include those compounds known technically as sodium copper chlorophyllin, sodium magnesium chlorophyllin, sodium nickel chlorophyllin, sodium iron chlorophyllin, sodium potassium copper chlorophyllin, potassium copper chlorophyllin, potassium magnesium chlorophyllin, potassium nickel chlorophyllin, potassium iron chlorophyllin, etc. The water soluble chlorophyll compounds should be present in the composition in amounts up to about 1.0% by weight of the final composition.

To demonstrate that dentifrice compositions comprising water soluble chlorophyll compounds, water insoluble calcium compounds as polishing agents, and water soluble alkali metal salts of the type herein described re lease more of the contained chlorophyll compound when employed in aqueous media than do compositions comprising only the watersoluble chlorophyll compounds and the water insoluble calcium compounds the following tests were run.

Several dentifrice compositions were prepared contain ing the various water insoluble calcium com ounds as polishing agents and the varying amounts of the several different water soluble alkali metal salts indicated in the table. Each one of the compositions contained 0.1% of water soluble potassium copper chlorophyllin. The values given in the table indicate the percent of the water soluble chlorophyll compound released when the compositions were mixed with water in the ratio of about one part of the dentifrice composition for four parts of Water.

TABLE Percent No. Dentifrice Composition pound Released Potassium copper chlorophyllin plus dicalcium phosphate dihydrate. Same as No. 1 plus 2.0% tetrasodium pyrophosphate .1.. Same as No. 1 plus 2.0% sodium tripolyphosphate. 4..-. Same as No. 1 plus 2.0% disodium pyr0pl1ospl1ate 5 Potassium copper chlorophyllin plus calcium carbonate Same as N 0. 5 plus 2.0% tetrasodium pyrophosphate Same as N o. 5 plus 2.0% sodium tripolyphosphate Same as N o. '5 plus 2.0% disodium pyrophosphate 9 Potassium copper chlorophyllin plus tricalcium phosp ate.

Same as No. 9 plus 2.0% tetrasodium pyrophosphate Same as No. 9 plus 5.0% tetrasodium pyrophosphate Same as N 0. 9 plus 2.0% sodium tripolyphospnate Same as N 0. 9 plus 5.0% sodium tripo1yphosphate. Same as N 0. 9 plus 2.0% disodium pyrophosphate Same as No. 9 plus 5.0% disodium pyrophosphate In addition to the essential ingredients above described the novel compositions of this invention may contain certain additional ingredients. Thus, the dentifrice compositions ordinarily will contain a detergent or cleansing ingredient. The amount of detergent and the particular detergent used may be the same as employed in conventional dentifrice preparations. Examples of suitable materials include soaps, i.e., water soluble salts of higher fatty acids, as well as synthetic detergents.

The amount of detergent used depends upon the particular one selectedand upon the amount of foaming action desired in the product. For example, if ordinary soaps are employed they may be used in amounts up to about of the final composition whereas such materials as synthetic detergents may be used in amounts up to about 8% of the final composition.

Furthermore, flavoring materials may be used to impart a pleasant taste to the compositions and to render the same more palatable. Suitable flavoring materials include oil of Wintergreen, oil. of peppermint, oil of spearmint, oil of eucalyptus, cloves, menthol, anise, thyme, soluble saccharine, etc.

In order to indicate even more fully the advantages and capabilities of the novel compositions of the present invention, the following specific examples of representative dentifrice compositions are set forth. The formulations have been set forth for illustrative purposes only and they are not intended to limit the scope of the invention in any manner. The pH value given in each example represents the hydrogen ion concentration of a. 2.0% Water slurry of the respective compositions.

Example I A dentifrice composition in paste form comprises:

Percent Dicalcium phosphate dihydrate 50.0 Sodium copper chlorophyllin 0.1 Tetrasodiumpyrophosphate 2.0 Carboxymethyl cellulose 1.5

Water, balance.

This composition has a pH of approximately 7.5.

Example II A dentifrice composition in paste form comprises:

Percent Dicalcium phosphate dihydrate 37.5 Calcium carbonate 12.5 Potassium copper chlorophyllin 0.1 Disodiurn pyrophosphate 3.0 Sodium alginate 1.2

Water, balance.

This composition has a pH of approximately 8.0.

Example III A dentifrice composition in paste form comprises:

Percent Commercial tricalcium phosphate 40.0 Sodium copper chlorophyllin 0.05 Sodium citrate 5.0

Sodium lauryl sulfoacetate 4.0 Irish moss 0.3

Glycerin 35.0 Oil of peppermint 1.0

Water, balance.

This composition has a pH of approximately 8.5.

Saccharine Water, balance.

This composition has a pH of approximately 8.8,

Example V A dentifrice composition in powder form comprises:

Percent Calcium carbonate 84.8 Sodium copper chlorophyllin 1.0 Saccharine 0.2 Sodium silicate 3.0 Powdered palm oil soap 8.0 Oil of Wintergreen 3.0

This composition has a pH of approximately 10.8.

Example VI A dentifrice composition in powder form comprises:-

Percent Dicalcium phosphate dihydrate 91.8 Sodium copper chlorophyllin 0.2 Sodium lauryl sulfate 3.0 Sodium tripolyphosphate 3.0 Oil of peppermint 2.0

This composition has a pH of approximately 8.5. As indicated in the preceding examples certain adjuvant materials may be incorporated in minor amounts in the novel compositions herein described. Thus, a binder or thickening agent may be present. The amount of binder used depends largely upon the particular material selected. If sodium alginate is used as the binder, it advantageously may be used in amounts up to about 3% of the final composition. Gum tragacanth may be used in amounts ranging from about 0.1% up to about 3%, based upon the finished product, while carboxymethyl cellulose may be used in even larger amounts, e.g., up to about 4% or even a little more. Similarly, such binders. as Irish moss and pectin may be used in relatively widely varied proportions.

Furthermore, ingredients such as titanium dioxide may be incorporated in the composition in amounts ranging up to about 2.0% to lighten the color of the finished composition.

The present invention, in the broadest aspects thereof, contemplates .the formulation of the novel dentifrice compositions in any desired physical form, e.g., in an aqueous form such as a cream or paste; as a dry powder; etc. A powdered dentifrice composition may be prepared readily and simply by mixingthe ingredients in the proper proportions in any desired order.

When preparing the novel compositions of this invention in an aqueous form all the liquid ingredients, e.g., water, ethanol and the like, are introduced into a vessel and thoroughly stirred to forma homogeneous mixture. The water soluble alkali metal salt material is added to the mixture after which the polishing agent, water soluble chlorophyll compound, and any desired adjuvant ingredients (flavoring ingredients, titanium dioxide, etc.) are introduced. If a detergent is employed in the composition itpreferably is introduced into the thoroughly mixed liquid ingredients prior to the introduction of the water soluble alkali metal salt.

While there has been disclosed and described what is at present considered to be the preferred embodiment of the present invention, it will be understood, of course, that many modifications and changes and substitutions may be made therein without departing from the true scope of the invention as defined in the appended claims.

Having thus described the invention, what is claimed is:

1. A dentifrice composition comprising at least one water insoluble calcium compound, a water soluble chlorophyll compound, and a water soluble material selected from the group consisting of alkali metal salts of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, citric acid, silicic acid, gluconic acid, and ethylene diamine tetraacetic acid.

2. A dentifrice composition comprising at least one water insoluble calcium compound, amounts up to about 1% of a water soluble chlorophyll compound, and a water soluble material selected from the group consisting of alkali metal salts of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, citric acid, silicic acid, gluconic acid, and ethylene diamine tetraacetic acid.

3. A dentifrice composition comprising a polishing agent consisting essentially of at least one water insoluble calcium compound, small amounts up to about 1% of a water soluble chlorophyll compound, and a water soluble material selected from the group consisting of alkali metal salts of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, citric acid, silicic acid, gluconic acid, and ethylene diamine tetraacetic acid.

4. A dentifrice composition in paste form comprising amounts up to about 1% of a Water soluble chlorophyll compound, about 20% to 95% of dicalcium phosphate dihydrate, a water soluble material selected from the group consisting of alkali metal salts of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, citric acid, silicic acid, gluconic acid, and ethylene diamine tetraacetic acid.

5. A dentifrice composition in powder form comprising amounts up to about 1% of sodium copper chlorophyllin,

about 20% to of a polishing agent consisting essentially of dicalcium phosphate dihydrate, amounts of up to about 10% of a water soluble material selected from the group consisting of alkali metal salt of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, citric acid, silicic acid, gluconic acid, and ethylene diamine tetraacetic acid.

6. A dentifrice composition comprising amounts up to about 1% of a water soluble chlorophyll compound, about 20% to 95% of a polishing agent consisting essentially of an insoluble inorganic calcium compound, and amounts up to about 10% of an alkali metal salt of ethylene diamine tetraacetic acid.

7. A dentifrice composition comprising amounts up to about 1% of a water-soluble chlorophyll compound, from about 20% to about 95% of a polishing agent consisting essentially of a water-insoluble inorganic calcium compound, and amounts up to about 10% of a water-soluble alkali metal phosphate.

References Cited in the file of this patent UNITED STATES PATENTS 2,191,199 Hall Feb. 20, 1940 2,216,816 Kuever Oct. 8, 1940 2,519,665 Klippert Aug. 22, 1950 2,647,073 Singer July 28, 1953 FOREIGN PATENTS 444,276 Great Britain Mar. 18, 1936 490,384 Great Britain Aug. 15, 1938 522,646 Great Britain June 24, 1940 601,801 Great Britain May 12, 1948 665,707 Germany Sept. 15, 1938 OTHER REFERENCES J. Amer. Dental Assn. March 1949, pp. 369-370. Rothemund: Glassers Medical Physics Year Book Publishers, 1948, p. 171. 

1. A DENTIFRICE COMPOSITION COMPRISING AT LEAST ONE WATER INSOLUBLE CALCIUM COMPOUND, A WATER SOLUBLE CHLOROPHYLL COMPOUND, AND A WATER SOLUBLE MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL SALTS OF ORTHOPHOSPHORIC ACID, PYROPHOSPHORIC ACID, TRIPOLYPHOSPHORIC ACID, CITRIC ACID, SILICIC ACID, GLUCONIC ACID, AND THEYLENE DIAMINE TETRAACETIC ACID. 